Unique effects of aerosol OT lamellar structures on the dynamics of guest molecules.

The behavior of lamellar structures of Aerosol OT (AOT) as hosts, vis-à-vis the flexible normal micelles and rigid nanochannels of Nafion membranes, has been investigated with two different fluorophores, [2,2'-bipyridyl]-3,3'-diol (BP(OH)2) and coumarin 102 (C102). Surprisingly, for BP(OH)2, a rise time is observed at intermediate emission wavelengths and not in the red edge of the fluorescence spectrum. A shoulder at 525 nm is observed in time resolved emission spectra (TRES) at initial times of BP(OH)2 in AOT lamellar structures. This feature is the signature of the monoketo (MK) tautomer, observed for the first time in a microheterogeneous medium. Also, the usually ultrafast single proton transfer in BP(OH)2 is retarded to an considerable extent in lamellar structures. The potential of this medium in promoting unusual intermediates is thus highlighted. This property may be ascribed to the rigidity of lamellar structures, compared to hosts such as regular micelles. However, studies using another fluorophore, coumarin 102 (C102), brings out the fact that these structures are significantly different from the rigid host, Nafion, as well. The absence of excited state proton transfer (ESPT) in this molecule in AOT lamellar structures indicates that it is not protonated, unlike in Nafion. Thus, the interfacial pH of lamellar structures is found to be significantly greater than that of Nafion nanochannels. From the time dependent Stokes shift (TDSS) of the emission spectra of C102, the relaxation time (0.85 ns) of interfacial water in lamellar structures is found to be an order of magnitude faster than that observed in Nafion nanochannels, in which H3O(+) ions have been substituted by different cations. Hence, this study demonstrates that AOT lamellar structures are rather unique hosts and that they behave very differently from conventional rigid and flexible hosts such as normal micelles and Nafion, respectively.

Anisotropic dynamics of guest molecules in aerosol OT lamellar structures.

The present work is focused on developing a description of an anisotropic microheterogeneous medium, exploiting the dynamics of a guest molecule. The medium in question is the lamellar structures formed in the aqueous layer of ternary mixtures containing aerosol OT (AOT), water and n-heptane. The guest used in this study is the fluorescent probe, coumarin 153 (C153). The dynamics of this molecule, within the lamellar structure, have been studied using a combination of steady state and time resolved fluorescence, as well as fluorescence correlation spectroscopy (FCS). The fluorophore is strongly solvatochromatic and so, the wavelength of excitation can be tuned so as to selectively excite fluorescent molecules residing in different regions of the microheterogeneous media, even if the spatial separation between these regions is below the diffraction limit. The excitation wavelength in the present experiments is chosen so as to exclusively excite those C153 molecules that reside in the hydrophobic region of the lamellar structures. This triggers two different modes of diffusion, one along and the other perpendicular to the bilayers of the AOT. Thus, the dynamics of the fluorescent probe provide an elegant manifestation of the anisotropy of the host medium.

Unusual binding of a potential biomarker with human serum albumin.

This study investigates the specific binding of a potential biomarker, [2,2'-bipyridyl]-3,3'-diol (BP(OH)2), with human serum albumin (HSA). The binding of BP(OH)2 at the two primary drug-binding sites on HSA (Sudlow's sites I and II) is explored by a competitive-binding study and monitored by considering the green-light emission from its diketo tautomer. Warfarin is used as a marker for site I and dansyl-L-proline (DP) as a competitor for site II. Steady-state and time-resolved fluorescence measurements affirm that neither of Sudlow's sites is the binding locus of BP(OH)2. To gain an idea regarding the probable binding site of BP(OH)2, we perform molecular-docking studies, which reveal a close proximity of the probe to Trp-214 in subdomain IIA of HSA. Confirmation of this contention is achieved by studying the quenching of the fluorescence of Trp-214 in the presence of BP(OH)2. Moreover, static quenching seems to be responsible for the depletion of the fluorescence of Trp-214, as manifested by the invariance of the intrinsic fluorescence lifetime of Trp-214, as a function of the concentration of BP(OH)2. Based on displacement and quenching studies, supported by molecular docking, we propose that BP(OH)2 binds in a cleft that separates subdomains IIIA and IIB, which is in close proximity to Trp-214.

Nanoconfinement of water layers in lamellar structures prepared in the presence and absence of organic solvent.

An attempt is made to draw a line of comparison between the extent of rigidity of the hydration layers bound to the interfacial region of lamellar structures of Aerosol OT (AOT, sodium bis(2-ethylhexyl) sulfosuccinate) in water, in the presence and absence of an organic solvent using POM, SAXS, cryo-TEM, and time-resolved fluorescence spectroscopy. These systems are ternary mixtures of AOT, water, and n-heptane containing lamellar structures in an aqueous layer at higher w(0) values (w(0) = 300 and 150) and a binary solution of 20 and 50% AOT in neat water (w/w). The solvation shells residing at the vicinity of these lamellar structures are monitored using two different coumarin probes (C153 and C500). It is intended to envisage a comparative solvation dynamics study of the restricted aqueous region confined in lamellar structures formed in ternary mixture and binary solution. Though steady state measurements show a similar microenvironment probed by the fluorophores in lamellar structures formed in the two different aqueous phases, temporal evolution of the solvent correlation function C(t) unveils the existence of lamellar structures with different degrees of confinement of water layers in these two systems. A slower relaxation of the restricted aqueous region in lamellar structures of binary solution signifies the presence of more rigid interfacially bound water layers at the lamellar interface than in the ternary mixture having a similar weight percentage of AOT in water. The present investigation concludes that the lamellar structures formed under two different conditions provide a similar hydrophobic environment with different extents of localized water populations at the lamellar interface as manifested by the solvent relaxation time in agreement with SAXS and cryo-TEM images.

Prototropism of [2,2'-bipyridyl]-3,3'-diol in albumin-SDS aggregates.

In this present investigation, attempt is made to use [2,2'-bipyridyl]-3,3'-diol (BP(OH)(2)) as a marker to study albumin-SDS interactions and to obtain structural information about these aggregates. It is also intended to contemplate the effect of these aggregates on the excited-state proton-transfer dynamics of BP(OH)(2). Steady-state and time-resolved fluorescence spectroscopic techniques are employed to elucidate the nature of interaction of two homologous carrier proteins, human serum albumin (HSA) and bovine serum albumin (BSA), with negatively charged surfactant sodium dodecyl sulfate (SDS). Both spectral and temporal behavior of BP(OH)(2) in these albumin-SDS aggregates strongly affirm an initial competitive binding of SDS in high-energy binding sites of albumin. Unlike normal SDS micelles, the absence of formation of the monocation of BP(OH)(2) at the negatively charged interface of SDS is rationalized by screening of the micellar interface in the presence of denatured protein which wraps around these surfactant aggregates. An enhanced extent of excited-state proton transfer is manifested by a corresponding increase in fluorescence quantum yield of BP(OH)(2) in these aggregates. Temporal evolution of BP(OH)(2) at different emission wavelengths fortifies the formation of normal micelles post saturation. All our observations are found to corroborate with the necklace and bead model proposed for protein-surfactant aggregates.

Selective recognition of fluoride and acetate by a newly designed ruthenium framework: experimental and theoretical investigations.

An effective anion sensor, [Ru(II)(bpy)(2)(H(2)L(-))](+) (1(+)), based on a redox and photoactive {Ru(II)(bpy)(2)} moiety and a new ligand (H(3)L = 5-(1H-benzo[d]imidazol-2-yl)-1H-imidazole-4-carboxylic acid), has been developed for selective recognition of fluoride (F(-)) and acetate (OAc(-)) ions. Crystal structures of the free ligand, H(3)L and [1](ClO(4)) reveal the existence of strong intramolecular and intermolecular hydrogen bonding interactions. The structure of [1](ClO(4)) shows that the benzimidazole N-H of H(2)L(-) is hydrogen bonded with the pendant carboxylate oxygen while the imidazole N-H remains free for possible hydrogen bonding interaction with the anions. The potential anion sensing features of 1(+) have been studied by different experimental and theoretical (DFT) investigations using a wide variety of anions, such as F(-), Cl(-), Br(-), I(-), HSO(4)(-), H(2)PO(4)(-), OAc(-) and SCN(-). Cyclic voltammetry and differential pulse voltammetry established that 1(+) is an excellent electrochemical sensor for the selective recognition of F(-) and OAc(-) anions. 1(+) is also found to be a selective colorimetric sensor for F(-) or OAc(-) anions where the MLCT band of the receptor at 498 nm is red shifted to 538 nm in the presence of one equivalent of F(-) or OAc(-) with a distinct change in colour from reddish-orange to pink. The binding constant between 1(+) and F(-) or OAc(-) has been determined to be logK = 7.61 or 7.88, respectively, based on spectrophotometric titration in CH(3)CN. The quenching of the emission band of 1(+) at 716 nm (λ(ex) = 440 nm, Φ = 0.01 at 298 K in CH(3)CN) in the presence of one equivalent of F(-) or OAc(-), as well as two distinct lifetimes of the quenched and unquenched forms of the receptor 1(+), makes it also a suitable fluorescence-based sensor. All the above experiments, in combination with (1)H NMR, suggest the formation of a 1:1 adduct between the receptor (1(+)) and the anion (F(-) or OAc(-)). The formation of 1:1 adduct {[1(+)·F(-)] or [1(+)·OAc(-)]} has been further evidenced by in situ ESI-MS(+) in CH(3)CN. Though the receptor, 1(+), is comprised of two N-H protons associated with the coordinated H(2)L(-) ligand, only the free imidazole N-H proton participates in the hydrogen bonding interactions with the incoming anions, while the intramolecularly hydrogen bonded benzimidazole N-H proton remains intact as evidenced by the crystal structure of the final product (1). The hydrogen bond mediated anion sensing mechanism, over the direct deprotonation pathway, in 1(+) has been further justified by a DFT study and subsequent NBO analysis.

Modulation of ground- and excited-state dynamics of [2,2'-bipyridyl]-3,3'-diol by micelles.

The binding of [2,2'-bipyridyl]-3,3'-diol (BP(OH)(2)) with ionic and neutral surfactants like cetyltrimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS), and Triton X-100 (TX-100) has been studied by steady-state and time-resolved fluorescence spectroscopy. The absorption as well as emission spectra of BP(OH)(2) are highly sensitive toward the variation of surfactant concentration and hydrophobicity of the environment. The fluorescent state of the diketo form gains stability in surfactant assemblies, leading to a red-shifted emission spectra. A sharp increase in the fluorescence quantum yield near critical micellar concentration (CMC) is encountered followed by saturation. This indicates a complete encapsulation of BP(OH)(2) in the micelles. The maximum fluorescence quantum yield in anionic SDS is rationalized by the formation of cationic fluorophore at the Stern layer. The increase in quantum yield in neutral TX-100 is attributed to higher microviscosity experienced by the fluorophore in the palisade layer. A direct support in favor of this argument in TX-100 is provided by the viscosity dependence exhibited by the probe in different concentrations of sucrose solutions. CTAB exhibiting only hydrophobic effect shows least increase in qunatum yield of BP(OH)(2) among all the surfactants. Time-resolved fluorescence study of BP(OH)(2) in micelles is used as a tool to monitor the extent of micellization in the lipophilic cavity. An increase in fluorescence quantum yield as well as lifetime of BP(OH)(2) upon micellization indicates an enhanced extent of ESIDPT in hydrophobic medium.